Substituted pyrrolidinones and piperidinones



' to twenty carbon atoms, an alkoxyalkyl group of three United States PatentO LChain'may have alkyl, aryl, and alkaryl.

- he'Xyl, phenyl, naphthyl,

' atoms; The carbon atomsin the Dchainmay have their may beyfour hydrogen atoms, four .to be joined together to f 3,132,149 SUBSTITUTED PYRROLIDINONES AND PlrE--- w NES This invention deals with specific substituted pyrrolidinones and pimridinones asnew compositions of matter. It further deals witha method for the preparation of these specific substituted pyrrolidinones and piperidinonesw I The compounds of this invention are prepared by reactwith an alcohol having the formula R OH. In the above formula, the symbol R represents a hydrogen atom, an alkyl group of one to eighteen carbon atoms, an aryl group of .up to ten carbon atoms, an aralkyl group of up to twelve carbon atoms, an alkarylalkyl group of up to ten carbon atoms, and an alkylaminoalkyl group of three'to eighteen carbon atoms provided that the amino group is a secondaryortertiary structure, that is, non-primary. .Alkyl, in the above definition, is to be construed.

to includecycloalkyl and alkyl cycloalkyl within the. *angeof carbonatoms previously set'forth Typical R representations are hydrogen, methyl, ethyl, butyl, octyl, decyl, dodecyL octadecyl, cyclopentyl, cyclohexyl, phenyl, naphthyl, benzyl, "phenylethyl, rnethylpheny1, methoxyethyl, methoxypropyl, propoxyethyl, butoXy-' ethyl, pentoxyethyl, N,N-dimethylaminoethyl, N,N-dipropylaminopropyl, morpholinopropyl and pyrrolidinoethyl.

The symbol R represents hydrocarbon groups'of one preferably alkyl, arylalkyl, cyclo- R may typically represent methphenylbutyl, cyclopentyl, cyclobutylphenyl groups, and the like.

to tencarbon atoms,

yl, butyl, octyl, benzyl D is a divalent chain remaiuingvalences satisfied byhydrogen atoms, by alkyl groups whose jtotal carbon atom content is no greater thanlS, or by combinations of hydrogen atoms and alkyl groups. When D contains twocarbon atoms, there are foufvalencesst'o be satisfied by hydrogen atoms,.alkyl groups, or combinationsthereofigvFor instance, there I alkyl groups,.three., hydrogen atoms and one alkyl group, two hydrogen atoms andfjtwo alkyl groups, or one hydrogen atom'andthree alkyli groupsi When, D contains threejcarbon atoms,

, there are sir; 'valences to be satisfied byhydrogen atoms,

alkyl groups, or combinations thereof and these valences maybe satisfied in a way analogous to the manner described above when D contains two carbon atoms. It is also'possible for the above-mentionedalkyl' ,substitu'ents rm carbocyclic rings; in conjunctionl withthe D chains When D'r'epresents a three" carbonchain R may representa'hydrogen atom in addi-. tion to thef'other embodiment, discussed previously. The alkyl substituents on thecarbonatoms of the D any possible spatial configurations, such as normal, iso, te'rtia y, and the like. These alkyl substitu ents may'also be straight chained orcyclic Typical 7 ofth'e alkyl substituents that may be used to satisfy the u remaining "valcnces of the carbon atoms in the Dchain v 35 3,6-dimethy1-3 5 5,5-din1'ethy1-6-h contaming two to three carbon VsPiroBBdimethYlbicYdo desirable, from the viewpoint-- reactants the specific pyrrolidinones and. piperidinones 4,5-dimethyl 7a-hydroxy- -5-hydroxy-2-pyrrolidinone, K 3,3-peutamethylene-2,3,3a,4,5,6,7,7a-octahydroindol-Z-one, 3-methyl-3,5-dipropyl S-hydroxy-Z-pyrrolidinone, 1- (2-phenylethyl) -3 ,3,S-trimethyl-S-hydroxy-Z-pyrrolidinone, 1 3,3,5 -trimethyl-5 -hydroxy-2-pyrrolidinone,

ing a compound havingtthe formula, I 15 3,5-dimethyl-3:neopentyl-5-hydro ry 2-pyrrolidinone,

V 1-(3-d1ethylam1nopropyl) -3,3,S-tnmethyl-S-hydroxy-Z- /1)\ pyrrolidinone, a 0 I-(Z-dimethylaminoethyl)-3,3,5-trimethyl-5-hydroxy-2- pyrrolidinone.

O f 20 1-benzyl-3,3,Sirimethyl-S-hydrdxy-Z-pyrrolidinone,

R 1 p-tolyl 3,3,S-trimethyl-5-hydroXy-2-pyrrolidinone,

,1- 3-dimethy1amiuopropyl) -3,5 -dimethy1-3 hydroxy-Z-pyrrolidinone,

1 -(3-methoxypropyl)-3,3,S-trimethyl-S-hydroXy 2-pyrrolidinone; V i r 3,5-dimethy1-3-heXy1-5-hydroxy-Z-pyrrolidinone, i

1-dodecyl-3,3,S-trimethyl-5-hydroxy-2-pyrrolidinone,

3,6-dimethyl-3-(2,2-dimethylpropyl)-6-hydroXy-2 piperidinone, A

-piperidinone, I 1,3,3,6-tetrainethyl-6-hydroxy-2-piperidinone, '1- (Z-dimethylaminoethyl) -3,3,6-trimethyl-6-hydroxy-2- piperidinone, 3,3,6-trimethyl-6-hydroxy-2-piperidinone,

-neopentyl-6-hydroxy-2-piperidinone,' 3,6-dihexy1-3-methyl-6-hydroxy 2-piperidinone, 1 p-tolyl-3,3,6-trimethyl-6-hydroXy-2-piperidinone, 1,5,S-trimethyl-6-hydroxy-2-piperidinone, 5,5-dimethyl-4-ethyl-6-hydroxy-2-piperidinone, 3,6-di-(2-methy1propyl)-3-methyl-6-hydroXy 2=pipe1-idi none, I Y l- (2-diethylaminoethyl) -5,S-dimethyl-6-hydroxy-2-pia peridin0ne,' 3,4-din1ethyl-3-hexyl-6-hydroxy 2 piperidinone,

ydroxy-2-piperidinone,

(2.2.1 )heptane-2, 3 [6'- 6'-hydroxy-2'-piperidinone]}, 3 ,4,4-trimethyl-6-hydroxy- 2-piperidinone, 3,5,5-trimethyl-6 hydroxy-2 iperidinone, M 3,6-dibutyl-5-methyl-6-hydroxy-2-piperidinone.

The ,piperidinone and in the present process 7- and a-oxonitriles. fi-oxonitriles and, by the corresponding S-hydrdxy-Z-pyrrolidinone.. and 6 T droXy-Z vention may then V having the formula R OH in'the presence of an alkali to be more fully described hereinafter. Thus, it is possi- It ispossible to start with 'yand cyclization and hydration, obtain -piperidino nes of this in.

or: G-hydroxy-Z-piperidinones. It is, of-course generally discussedhereto'fore. i

' 'The' other reactant employed in the has the formulaR OH'in which R 13 carbon atoms. R

-neopentyl-5- J V pyrrolidinone reactants employed J may. be obtained by cycliiation of -piperidinone reactants. 'Theproducts of thisin? be derived by reaction with a compound Way without the necessity S-hydroxy-Z-pyrrolidinone present invention. contains from 1 to may be an-alkyl group-of 11 tolS carbon atoms, a cycloalkyl group-of 4 m 8 carbon atorne,

butanol, hexanol, decanol, 'dodecanol, hex'adecanol,- and decanol,

aqueous 0.1 molarsolution has pfiofabout at least 9. Typical examples of the catalyst that may be u'sedare sodium, potassium, lithium, sodium methoxide,,;potas- 55 If the solvent is desired, there may beused water,.hydro-.

alkoxyalkylv group of 2 tolS .carbon atoms, a phenylalltyl group of 7 to 18 carbon atoms, an alkyl substituted phenylalkyl group of 8 018 carbon atoms, a phenoxyalkyl group of 7 to 18'carbon atoms, an alkyl substituted phenoxyalkyl group of 8 to 18 carbon atoms, a phenoxypolyalkoxyalkyl group of 8 to 18 carbon atoms, an alkyl substituted phenoxypolyethoxyalkyl group of? to 18 carbon atoms, or a hydroxyalkyl group of 2 to 18 carbon atoms;

When R represents a hydroxyalkyl group, the product will have the formula C 10 In all other instances, the product has the formula,

R ID.

Typical of the 11 01-1 reactants are methanol, ethanol,

octadecanol, methoxyethan'ol, methoxybutanol, methoxymethoxyhexadecanol, ethoxyethanol, 'ethoxy octanol, ethoxydodecanol, propoxypropanol, propoxyheptanol, propoxyundecanol, .butoxybutanol, butoxytetradecanol, hexox'yhexanol, hexoxydode'canol, octoxynonanol, octoxydecanol, monoxynonanol, decoxybutanoLdocarbon atoms in the alkylene chain with the alpha and.

omega positions somewhat preferred. 7 Thepresent reactionis conducted in the presence of a basic catalyst ranging in-amounts from .005 by weight to stoichiometric amounts, preferably employing amountsv of about 0.1 to 20%. by weight otthe total weight of the reactants. Suitable as .acatalyst are alkali metals..- and their carbonates, alkali and alkaline earth metal lower alkoxides, oxides and hydroxides, secondary amines, tertiary amines, and quaternary ammonium bases. Actually there may be employedlas -a catalyst'any base Whose sium butoxide, lithium ethoxide, magnesium ethom'de; I sodium oxide, potassium hydroxide, calcium oxide, bari um hydroxide, strontiunr hydroxide, sodium carbonate,

potassium carbonate,dimethylamine, diethylamine, trirnethylamine, tri'ethylamine, I triethanolarnine, ,octyldi:

methylarnine, Nmethylmorpholine,-. benzyltrimethylam monium hydroxide, I dibenzyldimethylammonium hydroxide, fdodecenyltriethylammonium hydroxide, and thelike;

' Temperatures in the range of 35 to 150 C., preferably I 50to110 C1 are employed. Thereaction-is conductcd within the temperature ranges ata temperature .where the compound RZOH is liquid or molten. Thereactionmay';

J beconduc'ted without the use of a solvent, but a solvent is: frequentlyjdesirable if the compound R OH "isneither,

liquidlnor molten w'thin the stated'temperature'ranges. 7 0

carbons, secondary or tertiary alcohols,. ehers nitriles, secondary amides and the like and preferably one that; t

I forms an azeotrope with water. vTlypically. these. may be benzene,- toluene, heptzine, isooctane, .isopropylare surssecondary butanol, tertiary butanol, methyl isobutylcarbinol, diisopropyl ether, dibutyl ether, acetonitrile, isobutyronitrile, dirnethylformamide, and the like.

The products obtained are pasty or crystalline solids or viscous liquids which are isolated generally by simply stripping on the lighter components. This is particularly I dimethylacetamide,

.so when only small amounts of catalyst are used. Otherwise, the catalystis neutralized with acids, such as hydrochloric and sulfuric, and the products are separated from the salts by extraction with suitable solvents which dissolve the product but not the salts, such as benzene,

I and the like.

The products of this invention exhibit herbicidal activity. The present compoundsare also eiiective miticidcs when employed in the normal concentrations according to standard procedures and areefiective in controlling killing armyworms according to usual techniques and using concentrations of two to three pounds per gallons of spray mix. Particularly outstanding in this respect are the 5-methoxy.-, the 5-(2-ethylhexoxy)-, and

the 5-dodecoxy- 3,3,5-trimethyl-2-pyrrolidinones.

The. present invention can be more fully understood by the following examples which are oltered by way of illustration and not'by way of limitation. Parts by Weight areqused throughout. I f

Example 1 5-hydroxy-3,3,5-trimethyl 2-pyrrolidinone .(90 parts) was added to methanol (120 parts) containing sodium hydroxide(0.5 part) at 50 C. When solutionwas complete, themixture was cooled to 10 C. A white solid product crystallized (7 4v parts), MP. 123.5 to 126 C.

A second crop (7 parts) had a MP. ofl123 to 127 C.

. The'melting point and mixed melting point of this compound With starting ,material showed that this simple act of recrystallization was sufficient to accomplish displacement of the hydroxyl byth'e methoxyl group. The product is identified as 5 methoxy-3,3,S-trimethyl-Z-pyrrolidinone and has the formula The product contains 8.91% nitrogen (theoretical 8.92%). Q V

In asimilar fashion, 5-methoxy-S methyl-Z-pyrIolidinoneis prepared from methanol and S-hydroxy-S-methyl- "2 'py'rrolidinone, S-ethoxy 3,5 dimethyl-3-(2,2-dimcthylpropyl)-2-pyrrolidinone is preparedfrom ethanol and 5- hydroxy-3,,5-dimethyl -:3 (2,2-dimethylpropyl) -2-pyrrolidinone, 7a propoxy 3 ,3 pentamethylene-2,3,3 a,4,5 ,6,7 ,7 a-j octahydroindol-Z-one is prepared from l-proponal and 7 ahydroxy 3,3' pentamethylene-2,3,3a,-4,5,6,7,7a-octahydroindol-2-one, 5-butoxy-4,5-dimethyl-2-pyrrolidinone is prepared from butanol and S-hydroxy 4,5-dimethyl-2-pyrrolidinone, and -5-metl1oxy 1,3 ,3 ,5 -te t'ramethyl-2-pyrrolidinone is. prepared from methanol; and 5-hydroxy-1-,3,3,5- m *z'py r'olidinone. I

, 'It -is .also possibleto'obtain the above'adduct from the:

Y crude hydroxylactam prepared. from the ketonitrile and water in methanohsolution. The desired product separates directly from thereactionmixture. Thus, 2,2-dimethyl-4-oxopentanonitrile :(32 parts); methanol (50 parts), water (2 parts), and sodium hydroxide (0.5 part) 4 ;were mixed j and allowed to stand at room temperature for four days. Crystals began to separate after the first day. The mixturewas stripped under reduced pressure and the'residuefwas washed several times with acetone.

The first. crop hadMP. of 10 8 to C. The product p Example 3 V 5-hydroxy-3,3,5-trimethyl-2-pyrrolidinone (90 parts) and 2-ethylhexanol (400 parts) were heated at 70 C. for

24 hours in the presence of sodium methoxide (0.4 part) The reaction mixture was then stripped under reduced pressure to apot temperature of 70 to 880 C. (1.0 mm). This removed the Water and excess Z-ethylhexanol. The residue is identified as the compound 5-(2-ethylhexoxy)- 3,3,5-trimethy1-2-pyrrolidinone.

The. product contains 6.10% nitrogen (theoretical In a similar fashion are prepared 5-isooctoxy-3,3,5-trimethyl-Z-pyrrolidinone from isooctyl alcohol and 5-hydroxy-3,3,5-trimethyl-2-pyrrolidinone, 5-benzyloxy-3,5-dimethyl-3-hexyi-2-pyrrolidinone from benzyl alcohol and 3,5-dimethyl-3-hexyl-5-hydroxy-2-pyrrolidinone, and 6- pentoxy-S,5-dixnethyl-2-piperidinone from 6-hydroxy-5,5-

Example 4 5-hydroxy-3,5,5-trimethyl-2-pyrrolidinone (28.6 parts) and diethylene glycol (10.4 parts), benzene (100 parts by volume) and sodium methoxide (0.2 part) are boiled under reflux in an apparatus topped by aDe-an-Stark water separator. When the theoretical amount of water (3.6 parts) is separated, the mixture is stripped under reduced pressure to a pot temperature of 70/ 1 mm. The product which remains is the desired material, 1,7- bis-(3,3,S-trimethyl-Z-pyrrolidinon-S-yl) 1,4,7-trioxaheptane.

In a similar fashion, are prepared 5-octadeeyloxy-3, 3,5- trimethyl-Z-pyrrolidinone from octadecanol and 5-hydroxy-3, 3,5-trimethy1- 2 pyrrolidinone, 1,6 bis(4,5-dimethyI-Qpyrrolidinon-S-yloxy)hexane from 1,6-hexanediol and 4,S-dimethyl-5-hydroxy-2-pyrrolidinone, S-hexadecyloxy-3,5-dihexyl-3-methyl-2-pyrrolidinone is obtained from hexadecanol and 5-hydroxy-3,5-dihexyl-3-methyl-2- pyrrolidinone, and 6-octoxy-1,3,3,6-tetramethylpiperidinone is obtained from octanol and 6-hydroxy-1,3,3,6-tetramethylpiperidinone.

We claim:

1. A composition of matter from the class consisting of 6 and in which R is a member of the group consisting of hydrogen, alkyl of one to eighteen carbon atoms, phenyl, naphthyl, phenylalkyl of up to eighteen carbon atoms, alkylphenylalkyl of up to thirty carbon atoms, alkoxyalkyl of three to twenty-four carbon atoms, hydroxyalkyl of two to twelve carbon atoms, and alkylaminoalkyl of three to eighteen carbon atoms, R is a hydrocarbon group of one to ten carbon atoms from the class consisting of alkyl, phenylalkyl, cycloalkyl, phenyl, naphthyl, and alkylphenyl, R is a member from the class consisting of alkyl of one to eighteen carbon atoms, cycloalkyl of four to eight carbon atoms, alkoxyalkyl of two to eighteen carbon atoms, phenylalkyl of seven to eighteen carbon atoms, alkyl substituted phenylalkyl of eight to eighteen carbon atoms, phenoxyalkyl of seven to eighteen carbon atoms, alkyl substituted phenoxyalkyl of eight to eighteen carbon atoms, phenoxypolyalkoxyalkyl of eight to eighteen carbon atoms, and alkyl substituted phenoxypolyethoxyalkyl .of nine to eighteen carbon atoms, R is an alkylene of two to eighteen carbon atoms, and D is a divalent hydrocarbon chain containing two to three carbon atoms, the remaining valences of said two to three carbon atoms of said D are satisfied by members of the group consisting of hydrogen, alkyl having a total carbon atom content of up to eighteen and combinations of said hydrogen and said alkyl.

2. As a composition of matter, 5-methoxy-3,3,5-trimethyl-Z-pyrrolidinone.

3. As a composition of matter, 5-(2-ethy1hexoxy)-3,3,5- trimethyl-Z-pyrrolidinone.

4. As a composition of matter, 6-pentoxy-5,5-dimethyl- 2-piperidinone.

5. As a composition of matter, 1,7-bis-(2-pyrro1idinon- S-yl) -1,4,7-trioxaheptane.

6. As a composition of matter, 5-benzyloxy-3,5-dimethyl-3-hexyl-2pyrrolidinone.

References Cited in the file of this patent .UNITED STATES PATENTS Seeman et a1 Oct. 6, 1953 Schindler et a1. June 19, 1956 OTHER REFERENCES 

1. A COMPOSITION OF MATTER FROM THE CLASS CONSISTING OF
 4. AS A COMPOSITION OF MATTER, 6-PENTOXY-5,5-DIMETHYL2-PIPERIDINONE. 